Detergent compositions



2,932,615 Patented Apr. 12, 1960 DETERGENT COMPOSITIONS Edward S. Blake, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application February 19, 1957 Serial No. 641,045

7 Claims. (Cl. 252-135) The present invention relates to novel detergent ,compositions containing surface-active agents which are condensation products of glycerol-1,3-dialkyl ethers and ethylene oxide.

This application is a continuation-in-part of my copending application Serial No. 323,337, filed November 29, 1952, now' abandoned, directed to superior surfaceactive agents prepared by the condensation of ethylene oxide with a specific class of glycerol-1,3-dialkyl ethers.

It is the principal object of the instant invention to provide novel detergent formulations containing the aforesaid stuface-active agents in combination with various builders, and compositions as hereinafter more fully exemplified.

It is a further object of this invention to provide novel wetting agents or detergents, particularly novel nonionic surface-active reaction products of a glycerol-1,3-dialkyl ether and ethylene oxide.

It is a further object of this invention to provide a process for producing the novel reaction products referred to in the foregoing object.

Still further objects and advantages of this invention will become apparent from the following description and the appended claims.

More specifically the present invention relates to detergent compositions wherein the surface-active agent is selected from the group of chemical compounds having the structural formula:

H2-COR H-oo-0,H, on

HzCO-R' where R and R are alkyl radicals having a straight or branched-carbon chain and containing from 1 to 20 carbon atoms, for example, a methyl, ethyl, n-butyl, secbutyl,"octyl, methyl isobutyl carbinyl, decyl or cetyl radical, and x is a number from 5 to 25. In the above formula R and R may represent identical or dissimilar alkyl radicals.

The present invention is more particularly directed to detergent compositions wherein the surface-active compounds having wetting or detergent properties are selected from the group of compounds having the structural formula:

H3CO-R" where R" and R' are identical or dissimilar alkyl radioals having a straight or branched-carbon chain and which contain from 6 to 16 carbon atoms, preferably branched-chain alkyl radicals in which the carbon atom attached to the oxygen atom has two hydrogen atoms, and x is a number from 5 to 25, preferably 10 to 20. The efliciency of such compounds as wetting agents or detergents depends on the number and arrangement of carbon atoms in the alkyl radicals and the value of the number x. For example, if all other factors are constant,

the efliciency of the compounds as Wetting agents or detergents increases as the number of --(OC H groups increases up to a maximum and then begins to decrease. Similar changes are noted in the compounds when the number of carbon atoms in the alkyl radicals increase from 6 to 16. A particularly useful class of compounds of this invention, which are suitable as wetting agents or detergents, is the class of compounds which have the formula:

where x is a number from 10 to 20 and where the carbon atoms of the C H radicals attached to the 1,3-oxygen atoms of the glycerol residue have two hydrogen atoms.

The surface-active materials disclosed hereinabove vary in physical properties from viscous liquids to pasty solids or gel-like solids depending on the number of carbon atoms in the alkyl radicals and the number of polyoxyethylene groups in the molecule. The products which contain the larger alkyl radicals or larger number of polyoxyethylene groups generally are pasty or gel-like solids.

These surface-active compounds are suitably prepared, in general, by condensing ethylene oxide, in the substantial absence of oxygen and in the presence of an alkaline catalyst or condensing agent, with a glycerol-1,3-dialkyl ether having the structural formula:

H2O-O-R where R and R have the same significance as hereinbefore given. The preferred starting glycerol-1,3-dialkyl ethers are those which have the structural formula:

where R" and R have the same significance as hereinbefore given. The glycerol-1,3-dialkyl ethers which are used for preparingthe preferred chemical compounds of this invention are those having the structural formula:

H7C0CsH 7 'where the carbon atoms of the C H radicals attached to the 1,3-oxygen atoms of the glycerol residue have two hydrogen atoms.

In carrying out the process the ethylene oxide can be employed in amounts ranging from 5 to 25 mols per mol of the glycerol-1,3-dialkyl ether, preferably in amounts ranging from 10 to 20 mols per mol of such ether to prepare compounds which are useful as wetting agents or detergents. A substantially quantitative reaction between the reactants is obtained. For best results it is preferred to add the ethylene oxide to the glycerol-1,3- di'alkyl ether slowly, usually over a period of about 1 to 10'hours depending on the total amount of the ethylene oxide used.

The reaction is suitably carried out by purging the reactants completely or substantially completely of air or oxygen and then maintaining the reactants in an atmosphere which is substantially free of oxygen. This may be accomplished, for example, by passing a stream of nitrogen gas through a reaction vessel containing the glycerol-1,3-dialkyl ether until the ether is substantially free of oxygen and then maintaining an atmosphere of nitrogen gas inthe reaction vessel during the addition of the ethylene oxide and during the subsequent reaction between the reactants.

For best results the reaction between the ethylene oxide and the glycerol-1,3-dialkyl ether is carried out in the presence of an alkaline catalyst or condensing agent such as an alkali metal hydroxide, for example, NaOH or KOH or an alkali metal alcoholate such as sodium or potassium methylate or sodium or potassium ethylate. The amount of such catalyst used may be varied considerably. Generally, satisfactory results are obtained by using from about 0.5 to 3% by weight of the catalyst based on the glycerol-1,3-dialkyl ether. V

The reaction may be carried out in a closed vessel at V atmospheric pressure or relatively low super-atmospheric pressures, for example, a pressure ranging from 1 atmosphere to 10 atmospheres. The reaction may be carried out over a relatively wide temperature range. A suitable temperature range for most purposes is between about 70 and about 200 C., and preferably between about 100 and about 160 C.

In order to maintain optimum control of the temperature during the reaction it is preferred to stir the reactants, particularly during the early stages of the reaction when the first or second mol of ethylene oxide is introduced into the reaction zone.

The glycerol-1,3-dialkyl ethers employed in the processes of this invention may be prepared by slowly adding epichlorhydrin to an alkanol solution of a sodium or other alkali metal alcoholate of an alkanol containing from 1 to 20 carbon atoms while maintaining the temperature between about 100 and about 130 C. After the epichlorhydrin is added the temperature may be raised to from about 150 to about 200 C. until the reaction is complete. The product is thenwashed with water to remove dissolved alkali metal salts and alcoholate and is then vacuum distilled.

Afurther understanding of the surface-active products and processes will be obtained from the following specific examples which are intended to illustrate this invention but not to limit the scope thereof, parts and percentages being by Weight unless otherwise specified.

EXAMPLE I (a) Preparation of.glycerol-1,3-di(2-ethylhexyl) ether Forty-six grams of sodium -(2 mols) were dissolved under a blanket of nitrogen gas in 850 cubic centimeters of Z-ethylhexyl alcohol with stirringwhile heating at 150 C. The reaction mass was cooled to 104 C. and

. 78 cubic centimeters (1 mol) of epichlorhydrin were added dropwise with stirring over a period of one-half hour. The temperature of the reaction mixture rose to 120 C. during this period of time and the temperature was finally raised to 174 C. by heating. The reaction mixture was cooled to room temperature and was then washed with 500 cubic centimeters of water to remove dissolved salts and unreacted sodium Z-ethylhexyl alcoholate. The resulting product was washed again with 250 cubic centimeters of water and was then vacuum distilled. One hundred forty-three and seven-tenths grams of the glycerol-l,3-di(2-ethylhexyl) ether were collected at a temperature of 192-194" C. and at a pressure of 1,-8 millimeters of mercury absolute. This product gave'an acetyl number of 5.28% hydroxyl as compared to -atheoretical number of 5.37%.

(b) Preparation polyoxyethylene derivative of glycerol- ],3-di(2-ethylhexyl) ether 75' apsasie through the system. Ethylene oxide was introduced into the flask, which was maintained in a blanket of nitrogen I where Q is an average of five (5 )--O-C H (polygas, over a period of 5 hours while the contents of the flask were maintained at l'15l25 C. until a weight gain of 67.0 grams was obtained, which weight gain corresponded to the introductionof 5 mols of ethylene oxide per mol of the glycerol-l,3-di(2-ethylhexyl) ether. Fifty grams of the product were removed and this product consisted of a mixture of compounds having the structural formula:

C2H5 .Hr-(|3O .CHzOH-CrHw 11-o- '-or H2C-O-.CHz-C|HC4Ha OzHs oxyethylene) groups. Part of the product remained as an amber liquid and part of the productsolidified to an amber pasty solid on cooling. These products dissolved or dispersed in water at low concentrations. 7

EXAMPLE. II

The balance of the product remaining (113 grams) after the removal of grams as described in the last paragraph of Example -I was treated with 47 grams of ethylene oxide over a period of 2 hours while maintaining the reaction mixture at a temperature of 125 to 135 C. The procedure used was the same as described in the last paragraph of Example I. The product thus obtained contained 1O mols of ethylene oxide for each mol of glycerol- 1,3-di-(2-ethylhexyl) ether and consisted of a mixture of products having the structural formula:

CzHs

where R is an averag of ten (10) OC H (polyoxyethylene) groups Fifty grams of this product were removed fromthe remainder of the reaction mixture and were allowed to cool. Part of this product remained as an amber liquid while the major portion solidified to form a pasty amber solid. These products dissolved or dis- 7 persed in water in concentrations of at least 0.5%

Ninety grams 0.304 mol) of glycerol-l,3-di(2- ethyl- EXAMLE 111 (polyoxyethylene) groups. Fifty grams of this product were removed from the remainder of the reaction mixture and were allowed to cool. Substantially all of the product solidified to .form a pasty solid which dissolved or. dispersed .in waterinconcent'rations of at least 0.5

'the procedure set forth in the last paragraph of Example I. The resulting product contained 18.9 mols of ethylene oxide per mol of glycerol-1,3-di(2-ethylhexyl) ether and consisted of a mixture of compounds having the structural formula:

where Z represents an average of eighteen and nine- ;tenths (18.9) --O-C H (polyoxyethylene) groups.

On cooling the reaction mixturethe product solidified to an amber pasty solid which was soluble or dispersible in water at concentrations of at least 0.5%.

EXAMPLE v The products prepared according to Examples I through IV, hereinafter referred to as products A, B, C and D, respectively, were tested at various concentrations as wetting agents using the Draves-Clarkson test described on pages 162-165 of the 1935-1936 American Association of Textile Chemists and Colorists Yearbook. The following table shows the results obtained at various specific concentrations and a comparison with known wetting agents.

Draves wetting [In seconds at concentrations indicated] Product 0.5% 0.25% 0.125% 0.062% 0.031%

l Condensation product of 100 parts of tertiary dodecyl mercaptan and 228 parts of ethylene oxide.

1 Sodium dodecyl benzene sulionate.

superior as a wetting agent, at normal concentrations, to

sodium dodecyl benzene sulfonate, which is a commercial product, and is also superior, as a wetting agent, at lower concentrations, to the condensation product of 100 parts by weight of tertiary dodecyl mercaptan and 228 parts by weight of ethylene oxide.

EXAMPLE VI The products prepared according to Examples I through IV, hereinafter referred to as products A, B, C and D, respectively, were also tested as detergents according to the detergency test described in an article by Jay C. Harris in a series of articles in the publication Soap and Sanitary Chemicals for August and September 1943. The detersive efiectiveness of each product in the following table was compared with that of a commercially avail- 6 able synthetic detergent known to the trade as Gardinol WA which is a sodium salt of a sulfated fatty alcohol and is used as a reference equal to 100.

Detergency Percent Gardinol Product per se Detergent Com- Product position 1 Water Water Water Water Hardness, Hardness, Hardness, Hardness, 50 p.p.m. 300 p.p.m. 50 p.p.m. 300 p.p.m.

1 Detergent composition consisted of 20% of the product, 1% of purified carboxymethyl cellulose, 40% tetra sodium pyrophosphate, 19% soluble starch and 20% soda ash.

The foregoing table indicates that products B, C and D which contain 10 mols or more of ethylene oxide are generally superior to Gardinol WA as detergents when such products are used alone or in a detergent composition with builders, and also are superior to Gardinol WA at various water hardnesses. The table also indicates that of the products tested product C gives the best detergency.

Other suitable built detergent formulations employing the glycerol-1,3-dialkyl ethers disclosed above can be prepared according to the following general limitations, wherein the relative quantity of each material is in parts by weight. Suitable formulations contain (1) from about 10 to about 25 parts of the reaction products of glycerol- 1,3-dialkyl ethers, wherein the alkyl radicals each contain from 6 to 16 carbon atoms, with from 10 to 20 moles of ethyleneoxide per mole of said ethers, (2) from about 20 to about 60 parts, on an anhydrous basis, of a sodium polyphosphate, such as tetrasodium pyrophosphate, sodium tripolyphosphate, and mixtures thereof, (3) from about 10 to about 25 parts, on an anhydrous basis, of an alkaline material selected from the class: consisting of sodium carbonate, sodium bicarbonate, and mixtures thereof, (4) up to about 20 parts of starch, (5) up to about 25 parts, on an anhydrous basis, of a sodium sili cate having a ratio of Na O:SiO of from about 1:2 to about 123.2, and (6) from about 0.1 to about 5 parts of carboxymethyl cellulose. The formulation may also contain minor amounts of perfumes, anti-tarnish agents, and the like. More specifically the instant built detergent formulations can be illustrated by the following examples, wherein the listed materials are in parts by weight of the composition.

Example VII VIII IX Surface-active products 1 20 15 15 tetrasodium pyronhnsnhatn 40 20 sodium trlpolyphosphate. 40 20 sodium car 15 20 20 starch 14 sodium silicate (N8.g02SiO2=113.2) 10 24 24 carboxymethyl cellulose 1 1 1 Product 0 from Example III (condensation product of glycerol 1,3-di(2-ethylhexyl) other with 15 mols of ethylene oxide).

7 ylene oxide with '1 mol of ajglycerohLB-diallryl ether :having the structural formula: V

Hi-(J-O-R" HG-H M V ni-o-o-ua where R" and R' are alkyl radicals each containing from 6- to 16 carbon atoms, a sodium polyphosphate selected from the group consisting of tetrasodium pyrophosphate, sodium tripolyphosphate and mixtures thereof, soda ash, and carboxyrnethyl cellulose, said components being present in about the ratio of 1:2:1:0.05 in parts by weight. n p

2. A detergent composition consisting essentially of the reaction product of about 10 to about mols of ethylene oxide with 1 mol of a glycerol-1,3-dialkyl ether having the structural formula:

HCOH

. vHiC-(').-R"' where R and R' are alkyl radicals each containing from 6 to 16 carbon atoms, tetrasodium pyrophosphate, soda ash, and carboxymethyl cellulose, said components being present in about the ratio of 1:2 :1:0.05 in parts by weight.

3, A detergent composition consisting essentially of the reaction product of about 10 to about 20 mols of ethylene oxide with 1 mol of a compound having the structural formula:

where the carbon atoms of the C Hi radicals attached reactionproduct of about 10 to about 20 mols of ethylene oxide with 1 mol of glycerol-1,3-di(2-ethylhexyl) ether, tetrasodium pyrophosphate, soda ash, and carboxymethyl cellulose, said components being present in about the ratio of 1:2:1:0.05 in parts by weight.

5. A detergent composition consisting essentiallyof the reaction product of about 15 mols of ethylene oxide with 1 mol of glycerol-1,3-di(2*ethylhexy1) ether, tetrasodium pyrophosphate, soda ash, and carboxymethyl cellulose, said components being present in about the ratio of 1:2: 1:0.05 in parts by weight.

6. A detergent composition comprising about 20 weight percent of the reaction product of about 15 mols of ethylene oxide with l mol of glycerol-1,3-di(2-ethylhexyl) ether, about 40 weight percent of tetrasodium pyrophosphate, about 20 weight percent soda ash, about 19 weight percent soluble starch, and about 1 weight percent of carboxymethyl cellulose.

7. A detergent composition consisting essentially of (a) between about 10 and about 25, parts by weight of the reaction product ,of about 10 to about 20 mole or ethylene oxide with 1 molof 'g'lycerolalj-dialkyl ether having the structuralrformulaa where R" and R' are alkyl'radicals each containing from 6 to 16 carbon atoms, (b) between about 29 and about parts by weight of a sodium polyphosphate selected from the group consisting of tetrasodium pyrophosphate and sodium tripolyphosphate and mixtures thereof, (0) between about 10 and about 25 parts by weight of an alkaline material selected from the group consisting of sodium carbonate, sodium bicarbonate and mixtures thereof, and (d) between about 0.1 and about 5 parts by Weight of carboxymethyl cellulose.

References Cited in the file of this patent UNITED STATES PATENTSv Butler 

1. A DETERGENT COMPOSITON CONSISTING ESSENTIALLY OF THE REACTION PRODUCT OF ABOUT 10 TO ABOUT 20 MOLS OF ETHYLENE OXIDE WITH 1 MOL OF A GLYCEROL-1,3-DIALKYL ETHER HAVING THE STRUCTURAL FORMULA: 